Fluorinated cyclopenta[b]naphthalenes and their use in liquid-crystal mixtures

ABSTRACT

The invention relates to compounds of the formula (I) and also liquid-crystal mixtures comprising these compounds, and their use in liquid-crystal displays:  
                 
 
     in which  
     R 1  is H, F, CF 3 , OCF 3 , OCF 2 H, OCFH 2 , an alkyl radical or alkyloxy radical or an alkenyl radical or alkenyloxy radical,  
     R 2  is H, an alkyl radical or alkyloxy radical or an alkenyl radical or alkenyloxy radical,  
     M 1  and M 2  are —C(═O)O—, —OC(═O)—, —CH 2 O—, —OCH 2 —, —OCF 2 —, —CF 2 O—, —C≡C—, —CH 2 CH 2 —, —CF 2 CF 2 —, —CF═CF—C(═O)O— or a single bond  
     A 1  and A 2  are α-1,4-diyl, unsubstituted or mono- or disubstituted by F; where α is: phenylene cyclohexane, 1-cyclohexene,  
     or 1,3-dioxane-2,5-diyl  
     m and n are zero or 1; m+n=0 or 1  
     L 1 , L 2 , L 3 , L 4  and L 5  are H or F.

[0001] More and more applications of LCDs—for example, use in automobiles, where temperatures across a range from −40° C. to 100° C. may readily occur, and also for portable devices such as cell phones and notebook PCs—are requiring liquid-crystal mixtures combining a very wide range of operating temperatures with a very low threshold voltage.

[0002] Consequently there is an ongoing demand for new, appropriate liquid-crystal mixtures and components of such mixtures. As described in Ichinose et al. (IDW,00, Abstr. LCT4-3) or in DE-A-100 50 071, the search is on for materials possessing at the same time both high optical anisotropy (Δn) and low rotational viscosity, along with other parameters such as, for example, high absolute dielectric anisotropy (Δε) values, in addition to further application-relevant parameters.

[0003] It is an object of the present invention, therefore, to provide novel components for use in nematic or cholesteric or chiral smectic liquid-crystal mixtures which possess high absolute dielectric anisotropy values in combination with a favorable viscosity/clearing point relationship. Moreover, the compounds should be highly stable to light and UV and also to heat. Furthermore, they should be suitable for realizing high voltage holding ratios (VHRs). In addition, they should be readily available synthetically and thus potentially inexpensive.

DESCRIPTION OF THE DRAWINGS

[0004] For the purpose of illustrating the invention, the drawing provides additional information, which helps to define the invention.

[0005]FIG. 1 is a voltage/response time curve, which illustrates the requirement for inverse mode operation.

[0006] It has now been found that these requirements are met by the fluorinated cyclopenta[b]naphthalenes of the formula (I)

[0007] in which:

[0008] R¹ is H, F, CF₃, OCF₃, OCF₂H, OCFH₂, an alkyl radical or alkyloxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkenyloxy radical having from 2 to 12 carbon atoms, in which also in each case one (nonterminal) —CH₂— group (which is not adjacent to an oxygen) may have been replaced by —O— or

[0009] C(═O)O—, one —CH₂— group may have been replaced by —C≡C— or cyclopropane-1,2-diyl and/or one or more H may have been replaced by F

[0010] R² is H, an alkyl radical or alkyloxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkenyloxy radical having from 2 to 12 carbon atoms, in which also in each case one (nonterminal) —CH₂— group (which is not adjacent to an oxygen) may have been replaced by —O— or —C(═O)O—, one —CH₂— group may have been replaced by —C≡C— or cyclopropane-1,2-diyl and/or one or more H may have been replaced by F

[0011] with the proviso that R² may not be H if R¹ is H, F, CF₃, OCF₃, OCF₂H or OCFH₂

[0012] M¹ and M² independently of one another are —C(═O)O—, —OC(═O)—, —CH₂O—, —OCH₂—, —OCF₂—, —CF₂O—, —C≡C—, —CH₂CH₂—, —CF₂CF₂—, —CF═CF—C(═O)O— or a single bond

[0013] A¹ and A² independently of one another are phenylene-1,4-diyl, unsubstituted or mono- or disubstituted by F; cyclohexane-1,4-diyl, unsubstituted or mono- or disubstituted by F; 1-cyclohexene-1,4-diyl, unsubstituted or monosubstituted by F; or 1,3-dioxane-2,5-diyl

[0014] m and n independently of one another are zero or 1; m+n=0 or 1

[0015] L¹, L², L³, L⁴ and L⁵ are H or F with the provisos that

[0016] a) at least one element from the group L¹, L², L³, L⁴, L⁵ is F

[0017] b) L² and L³ are only F if L⁴ and L⁵ are H

[0018] c) L⁵ is only F if L⁴is F and L¹ is H.

[0019] Preference is given to the compounds of the formulae (Ia) to (In):

[0020] The synthesis of the compounds of the formulae (Ig-(In) takes place in accordance with Scheme 1.

[0021] In this scheme 1

[0022] X is the radical -(M¹-A¹)_(m)-R¹, in which M¹ is preferably a single bond.

[0023] The compound (E1) is known from the literature:

[0024] 1,8-difluoronaphthalene [30389-93-6]{Mallory et al., J. Am. Chem. Soc. 96, 3536 (1974)}.

[0025] For the individual reaction stages it is possible to operate in analogy to the following literature references, hereby incorporated by reference.

[0026] a) 1.BuLi/KOtBu 2. DMF 3.H₃O⁺ DE-100 22 661.2

[0027] b) R₂CH(CO₂H)₂, piperidine, pyridine in analogy to J.Am.Chem.Soc. 80, 4949 (1958)

[0028] c) H₂/Pd (C) in analogy to WO94/26692

[0029] d) polyphosphoric acid in analogy to J.Med.Chem. 32(4), 757 (1989)

[0030] e) Et₃SiH/F₃CCO₂H in analogy to DE-A-198 40 447.

[0031] f) 1. Metalation in analogy to J. Chem. Soc. Perkin Trans. I 1995 2729, Synlett 1990, 747 2. Reaction with an X-electrophile (in analogy to Tetrahedron 37, 6551 (1996)); on this point see also Schemes 4 to 7.

[0032] Here and in the schemes below, an X-electrophile is to be understood as referring to a functional derivative, as an electrophile, by way of which the group X can be introduced directly as such; it also refers, however, to a functional derivative which by way of a reaction sequence permits the synthesis of a substituent corresponding to X. Examples of X-electrophiles with which X can be introduced directly as such are alkyl halides (for X=R¹ when m=0) or NFSI (for X=F). One example of a reaction sequence for introducing X is the reaction with trimethylborate to give the corresponding boronic acid (X=B(OH)₂), the oxidation of that acid to the phenol (X=OH) and the conversion of said phenyl into the trifluoromethoxy compound (X=OCF₃) by the method of Hiyama (Bull.Chem.Soc.Jpn.73, 471 (2000)). The phenol may also, for example, be reacted with carboxylic acid or carboxylic acid derivatives to give compounds in which X is R¹-A¹-C(═O)O—. Another example of reaction sequences for introducing X is the reaction of the lithium compound with iodine (X=I) followed by Suzuki reaction with mesogenic boronic acids (R¹-A¹-B(OH)₂) to give compounds in which X is R¹-A¹-.

[0033] By “mesogenic” in this context are meant well-known building blocks of liquid-crystal compounds, typically featuring a para-(alkyl) substituent on a phenyl ring [which may have further substituents, including rings such as cyclohexane, for example, in an appropriate position (e.g., para)].

[0034] For the compounds (Ia) and (Ib) it is possible to use the synthesis according to scheme 2.

[0035] In this scheme 2, x denotes 0 or 1

[0036] The starting materials (E2) are known from the literature:

[0037] x=0

[0038] 5-Bromo-2-methyl-2,3-dihydro-1H-indene [88632-84-2], 5-bromo-2-octyl-2,3-dihydro-1H-indene [150636-27-4], and 5-bromo-2-decyl-2,3-dihydro-1H-indene [176317-00-3]; further homologs can be prepared analogously.

[0039] x=1

[0040] These compounds can be prepared in analogy to those where x=0 but replacing 2-alkylmalonic acids in the synthesis analogous to EP-A-546338 by 2-(4-alkylphenyl)malonic acids or 2-(4-alkylcyclohexyl)malonic acids. The following derivatives are known from the literature; further homologs can be prepared analogously: diethyl 2-(4-methylphenyl)malonate [29148-27-4], diethyl 2-(4-ethylphenyl)malonate [29148-28-5], diethyl 2-(4-propylphenyl)malonate [3585-46-4), diethyl 2-(4-butylphenyl)malonate [29148-30-9], dimethyl 2-(4-pentylphenyl)malonate [205760-95-8], diethyl 2-(4-hexylphenyl)malonate [29260-15-9], diethyl 2-(4-methylcyclohexyl)malonate [22273-84-3], diethyl 2-(4-ethylcyclohexyl)malonate [155378-91-9], diethyl 2-(4-propylcyclohexyl)malonate [100599-81-3], diethyl 2-(4-butylcyclohexyl)malonate [135564-27-1].

[0041] For the individual reaction stages it is possible to operate in analogy to the following literature references, hereby incorporated by reference.

[0042] a) 1. Mg 2. Oxirane 3. H₃O⁺ 4. KMnO₄ 5. SOCl₂ in analogy to Larock, Comprehensive Organic Transformations, VCH Verlag, Weinheim 1989, ISBN 3-527-26953-3

[0043] b) H₂C=CH₂, AlCl₃, dichloromethane in analogy to EP-A-0 343 830

[0044] C) Pd (C), triglyme in analogy to Adcock, J. Am. Chem. Soc. 89, 386 (1967)

[0045] d) F-TEDA-BF₄, acetonitrile in analogy to EP-A-0 952 135

[0046] e) DAST, dichloromethane in analogy to EP-A-0 952 135

[0047] f) H₂, Pd/C, THF in analogy to EP-A-0 952 135

[0048] g) 1. metalation in analogy to J. Chem. Soc. Perkin Trans. I 1995 2729, Synlett 1990, 747 2. X-electrophile in analogy to Tetrahedron 37, 6551 (1996)); for this, see also schemes 4 to 7

[0049] The synthesis according to scheme 3 can be used for the compounds (Ic) to (If).

[0050] In this scheme 3

[0051] X is R¹-(A¹-M¹)_(m)-, where m can be 0 or 1

[0052] The starting material (E3) is known from the literature (J. Med. Chem. 1993, 36, 2819 U.S. Pat. No. 6,159,561). For the individual reaction stages it is possible to operate in analogy to the following literature references, hereby incorporated by reference.

[0053] a) 1. LDA 2. CH₃I in analogy to U.S. Pat. No. 6,159,561

[0054] b) Et₃SiH/F₃CCO₂H in analogy to U.S. Pat. No. 6,159,561

[0055] c) DDQ in analogy to U.S. Pat. No. 6,159,561

[0056] d) SeO₂, dioxane in analogy to Larock, Comprehensive Organic Transformations, VCH Verlag, Weinheim 1989, ISBN 3-527-26953-3

[0057] e) R²CH(CO₂H)₂, piperidine, pyridine in analogy to J. Am. Chem. Soc. 80, 4949 (1958)

[0058] f) 1. H₂, Pd/C in analogy to WO 94/26692 2. polyphosphoric acid in analogy to J. Med. Chem. 32(4), 757 (1989)

[0059] g) Et₃SiH/F₃CCO₂H in analogy to DE-A-198 40 447

[0060] h) metalation in analogy to J. Chem. Soc. Perkin Trans. I 1995 2729, Synlett 1990, 747 2. X-electrophile in analogy to Tetrahedron 37, 6551 (1996)); for this, see also schemes 4 to 7.

[0061] Generally speaking, cyclopenta[b]naphthalenes obtained in accordance with schemes 1, 2 and 3 and in which X=H (or Z5, Z7, Z14 and Z21 in schemes 1 to 3) may be reacted by metalation in this position and subsequent reaction with electrophiles (e.g., trimethylborate, DMF, CO₂, n-alkyl aldehydes, 4-n-alkylcyclohexanones, iodine, bromine) to give precursors from which the compounds of the formula (I) of the invention can be prepared (schemes 4 to 7).

[0062] The preparation of the compounds required for the syntheses according to schemes 4 to 7, examples being alkyl-, alkenyl- or alkoxy-substituted, optionally additionally fluorinated benzoic acids, cyclohexanecarboxylic acids (scheme 6) phenylacetylenes (schemes 5 and 6), phenylboronic acids (scheme 5), bromobenzenes (scheme 5), 2-alkylpropane-1,3-diols (scheme 7), and 4-alkylcyclohexanones (scheme 4) and their reactions are known to the skilled worker and are described, for example, in WO 96/00710, WO 96/30344, Liq. Cryst. 1995, 18, 1, Mol. Cryst. Liq. Cryst. 1991, 204, 43, Liq. Cryst. 1997, 23, 389, Synthesis 1996, 589, WO 92/11241, EP-A 0665825, J. Mater. Chem. 1999, 9, 1669 and Chem. Ber. 1985, 118, 3332. Appropriately substituted benzyl alcohols and (hydroxymethyl)cyclohexanes are R²-A²-CH₂OH (scheme 6) can be obtained, for example, from the corresponding benzoic or cyclohexanecarboxylic acids R²-A²-COOH by reduction with lithium aluminum hydride (general procedure: Organikum, VEB Deutscher Verlag der Wissenschaften, 15th ed., Berlin 1984, section 7.3.4). Their bromination with phosphorus tribromide (in analogy to J. Org. Chem. 1984, 49, 2534-2540) provides the benzyl bromides and/or (bromomethyl)-cyclohexanes R²-A²-CH₂Br required in scheme 6. Subsequent reaction with triphenylphosphine in xylene gives the triphenylphosphonium bromides R²-A²-CH₂-P(Ph₃)Br which are mentioned in scheme 7. Correspondingly substituted benzaldehydes and cyclohexanecarboxaldehydes R²-A²-CHO (scheme 7) are available, for example, by reducing the respective carboxylic ester R²-A²-COOR (Bull. Korean Chem. Soc. 1999, 20, 1373) or oxidizing of the aforementioned benzyl alcohols and (hydroxymethyl)cyclohexanes R²-A²-CH₂OH (Tetrahedron Lett. 1968, 30, 3363).

[0063] Starting from the 6-hydroxy-substituted cyclopenta[b]naphthalenes (scheme 6) it is also possible, for example, to prepare the corresponding 6-trifluoromethoxy-substituted compounds of the formulae (Ic) and (Id) (Bull. Chem. Soc. Jpn. 2000, 73, 471).

[0064] The synthesis of specific radicals X takes place, for example, in accordance with DE-A 19528085, DE-A 19532292 and DE-A 19654487. Inventive compounds of the formula (I) with a 1-cyclohexene-1,4-diyl or 2-fluoro-1-cyclohexene-1,4-diyl- or 4-fluoro-3-cyclohexen-1-yl unit are prepared as described in Liq. Cryst. 1997, 23, 69, DE-A 4427266, DE-A 19607996, DE-A 19528665 and EP-A 0736513. As far as the synthesis of specific radicals R¹ and R² is concerned, reference may also be made, for example, to U.S. Pat. No. 4,798,680 (for optically active compounds with a 2-fluoroalkyloxy unit) and EP-A 0 318 423 (for compounds containing cyclopropyl groups in the side chain).

[0065] The compounds of the formula (I) are used preferably in nematic or cholesteric liquid-crystal mixtures. The liquid-crystal mixtures of the invention comprise at least one compound of the formula (I), preferably in an amount from 1 to 40% by weight, based on the liquid-crystal mixture. They preferably comprise at least 3 further components. The selection of these further compounds (e.g., from the types listed in DE-A-19629812, pages 12 to 16) and the preparation of the liquid-crystal mixtures are familiar to the skilled worker.

[0066] The invention further provides a liquid-crystal display comprising these liquid-crystal mixtures. This liquid-crystal display preferably operates in IPS display mode (Kiefer et al., Japan Display '92, p. 547) or in VA display mode (Ohmura et al., SID 97 Digest, p. 845) or in ECB display mode (EP-A-0 474 062).

[0067] Preference is likewise given to using the compounds of the formula (I) in chiral smectic liquid-crystal mixtures. The liquid-crystal mixtures of the invention comprise at least one compound of the formula (I), preferably in an amount of from 1 to 40% by weight, based on the liquid-crystal mixture. They preferably comprise at least 3 further components. These components are preferably selected from the known compounds having smectic and/or nematic and/or cholesteric phases. The selection of these further compounds (e.g., from the types listed in DE-A-19857352) and also the preparation of the liquid-crystal mixtures are familiar to the skilled worker.

[0068] The invention also provides a liquid-crystal display comprising these liquid-crystal mixtures.

[0069] The invention is illustrated by the examples below.

EXAMPLE 1

[0070] A chiral smectic liquid-crystal mixture M1 having the melting point 7° C. is admixed with 10% by weight of the compound 4,5-difluoro-6-hexyl-2-pentyl-2,3-dihydro-1H-cyclopenta[b]naphthaline [(Ih) where R¹=hexyl, R²=pentyl; obtained from the reaction sequence according to scheme 1]. The resulting mixture has a melting point of 0° C. The voltage/response time curve (FIG. 1) has the minimum required for inverse mode operation (e.g., “Fast High Contrast Ferroelectric Liquid Crystal Displays and the Role of Dielectric Biaxiality” by J. C. Jones, M. J. Towler, J. R. Hughes, Displays, Volume 14, No. 2(1993) 86-93 or M. Koden, Ferroelectrics 179, 121(1996)); the values achieved are within the industrially relevant range and the mixture is suitable for practical use.

EXAMPLE 2

[0071] A nematic liquid-crystal mixture M2 consisting of 50% by weight of 1-(3,4-difluorophenyl)-4-(4-vinyl)cyclohexylcyclohexane and 50% by weight of 1-[4-(3-butenyl)cyclohexyl]-4-(3,4-difluorophenyl)cyclohexane is admixed with 20% by weight of the compound 2-propyl-5,6,7-trifluoro-2,3-dihydro-1H-cyclopenta[b]naphthalene [(Ib) where R²=propyl; obtained from the reaction sequence according to Scheme 3]; as a result of the addition of the compound of the invention, the dielectric anisotropy Δε has risen from 4.8 to 5.6. 

What is claimed is:
 1. A compound of the formula (I)

in which R¹ is H, F, CF₃, OCF₃, OCF₂H, OCFH₂, an alkyl radical or alkyloxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkenyloxy radical having from 2 to 12 carbon atoms, in which also in each case one (nonterminal) —CH₂— group (which is not adjacent to an oxygen), may have been replaced by —O— or —C(═O)O—, one —CH₂— group may have been replaced by —C≡C— or cyclopropane-1,2-diyl and/or one or more H may have been replaced by F R² is H, an alkyl radical or alkyloxy radical having from 1 to 12 carbon atoms or an alkenyl radical or alkenyloxy radical having from 2 to 12 carbon atoms, in which also in each case one (nonterminal) —CH₂— group may have been replaced by —O— or —C(═O)O—, one —CH₂— group (which is not adjacent to an oxygen) may have been replaced by —C≡C— or cyclopropane-1,2-diyl and/or one or more H may have been replaced by F with the proviso that R² may not be H if R¹ is H, F, CF₃, OCF₃, OCF₂H or OCFH₂ M¹ and M² independently of one another are —C(═O)O—, —OC(═O)—, —CH₂O—, —OCH₂—, —OCF₂—, —CF₂O—, —C≡C—, —CH₂CH₂—, —CF₂CF₂—, —CF═CF—C(═O)O— or a single bond A¹ and A² independently of one another are phenylene-1,4-diyl, unsubstituted or mono- or disubstituted by F; cyclohexane-1,4-diyl, unsubstituted or mono- or disubstituted by F; 1-cyclohexene-1,4-diyl, unsubstituted or monosubstituted by F; or 1,3-dioxane-2,5-diyl m and n independently of one another are zero or 1; m+n=0 or 1 L¹, L², L³, L⁴ and L⁵ are H or F with the provisos that a) at least one element from the group L¹, L², L³, L⁴, L⁵ is F b) L² and L³ are only F if L⁴ and L⁵ are H c) L⁵ is only F if L⁴ is F and L¹ is H.
 2. A compound as claimed in claim 1, corresponding to one of the formulae (Ia) to (In)


3. A liquid-crystal mixture, comprising one or more compounds as claimed in claim 1 in liquid-crystal mixtures.
 4. A liquid-crystal mixture, comprising one or more compounds as claimed in claim
 2. 5. The liquid-crystal mixture as claimed in claim 3, which comprises one or more compounds of the formula (I) in an amount of from 1 to 40% by weight, based on the liquid-crystal mixture.
 6. The liquid-crystal mixture as claimed in claim 3, which comprises at least three further components of smectic and/or nematic and/or cholesteric phases.
 7. The liquid-crystal mixture as claimed in claim 3, which is chiral smectic.
 8. The liquid-crystal mixture as claimed in claim3, which is nematic or cholesteric.
 9. A liquid-crystal display comprising a liquid-crystal mixture as claimed in claim
 3. 10. The liquid-crystal display, which is operated in ECB, IPS or VA display mode and comprises a liquid-crystal mixture as claimed in claim
 8. 11. The liquid-crystal mixture as claimed in claim 4, which comprises one or more compounds of the formula (I) in an amount of from 1 to 40% by weight, based on the liquid-crystal mixture.
 12. The liquid-crystal mixture as claimed in claim 4, which comprises at least three further components of smectic and/or nematic and/or cholesteric phases.
 13. The liquid-crystal mixture as claimed in claim 4, which is chiral smectic.
 14. The liquid-crystal mixture as claimed in claim 4, which is nematic or cholesteric.
 15. A liquid-crystal display comprising a liquid-crystal mixture as claimed in claims
 4. 16. The liquid-crystal display, which is operated in ECB, IPS or VA display mode and comprises a liquid-crystal mixture as claimed in claim
 14. 